EP3069697B1 - Method for manufacturing a polymer sheet for use as an immobilization element - Google Patents

Method for manufacturing a polymer sheet for use as an immobilization element Download PDF

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Publication number
EP3069697B1
EP3069697B1 EP16167658.0A EP16167658A EP3069697B1 EP 3069697 B1 EP3069697 B1 EP 3069697B1 EP 16167658 A EP16167658 A EP 16167658A EP 3069697 B1 EP3069697 B1 EP 3069697B1
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EP
European Patent Office
Prior art keywords
cross
polymer sheet
linking
polymer
radiation
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EP16167658.0A
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German (de)
English (en)
French (fr)
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EP3069697A1 (en
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Steven Cuypers
Bogdan Bogdanov
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Orfit Industries NV
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Orfit Industries NV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/10—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges for stereotaxic surgery, e.g. frame-based stereotaxis
    • A61B90/14—Fixators for body parts, e.g. skull clamps; Constructional details of fixators, e.g. pins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/10—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges for stereotaxic surgery, e.g. frame-based stereotaxis
    • A61B90/14—Fixators for body parts, e.g. skull clamps; Constructional details of fixators, e.g. pins
    • A61B90/18—Retaining sheets, e.g. immobilising masks made from a thermoplastic material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/01—Orthopaedic devices, e.g. splints, casts or braces
    • A61F5/04—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints
    • A61F5/05—Devices for stretching or reducing fractured limbs; Devices for distractions; Splints for immobilising
    • A61F5/058—Splints
    • A61F5/05841—Splints for the limbs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/37—Restraining devices for the body or for body parts, e.g. slings; Restraining shirts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/37—Restraining devices for the body or for body parts, e.g. slings; Restraining shirts
    • A61F5/3707—Restraining devices for the body or for body parts, e.g. slings; Restraining shirts for the head
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07—Stiffening bandages
    • A61L15/12—Stiffening bandages containing macromolecular materials
    • A—HUMAN NECESSITIES
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146—Porous materials, e.g. foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00526—Methods of manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/0045—Perforating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/009—Shaping techniques involving a cutting or machining operation after shaping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/0266—Local curing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B29K2021/006—Thermosetting elastomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0014—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
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    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
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Definitions

  • the invention relates to a method for manufacturing a polymer sheet for use as a non-invasive immobilization element for the immobilization of one or more body parts in a predetermined position and/or posture, as described in the preamble of the first claim.
  • immobilization elements for the immobilization of body parts are described for example in EP1854439 , EP1537831 , EP1582187 in the name of Orfit Industries. Immobilization elements are frequently used in numerous applications such as, for example, in rehabilitation, in orthopaedic applications, in the immobilisation of ligaments or bone structures that show injuries, with trauma or disease, where the immobilization element serves for supporting and immobilisation of ligaments and muscular structure in a predetermined position and/or posture. Furthermore, immobilization elements are extensively used in radiation therapy and diagnostic imaging.
  • an adequate immobilization of the body to be treated and an adequate and reproducible positioning of the body part undergoing treatment is of crucial importance in order to ensure that the radiation is directed at and limited to the body part to be treated, and that the risk of irradiating surrounding tissue is limited to a minimum.
  • a reproducible positioning is also of the utmost importance in fractionated therapy, in which a part of the body, after predetermined time intervals, is exposed to irradiation.
  • the immobilization element exhibits a high stability, by which is meant that the ability to move or reposition the body part, once immobilized, is limited to less than a few mm, preferably up to 1 - 2 mm or even less.
  • US 2008/0004368 discloses self-crosslinkable and photo-cross-linkable, biodegradable polymer materials, which, after injection into human tissue or bone to be repaired, are cured in situ in order to serve as a support for tissue and/or skeletal reconstruction.
  • the method, described in US 2008/0004368 for the production of such materials include the copolymerization of poly(propylenefumarate) with poly(caprolactone) diol, and provides a block polymer of poly(propylenefumarate) with poly( ⁇ -caprolactone).
  • the block copolymer is cross-linked by redox- or photoinitiation, with or without the addition of an additional cross-linking agent.
  • the copolymer is self-crosslinkable, without the need of a cross-linking agent to be added and photo-cross-linkable in the presence of UV radiation.
  • the relatively rigid poly(propylenefumarate) segment provides mechanical strength and crosslinkability while the poly( ⁇ -caprolactone) segment provides flexibility for the self-cross-linking.
  • US 6291543 relates to articles whose surface is cross-linked by exposure to UV radiation.
  • the articles are formed from an elastoplastic material (such as a polyester, polyamide, polyurethane, etc.), a cross-linking agent (for example, triallyl cyanurate), which is cross-linkable by free-radical polymerization, and a source of free radicals (for example, benzophenone), which generates free radicals upon exposure to UV radiation.
  • the article is particularly suitable for use in a catheter or other medical application. Only the top layer of the article is cross-linked, hence not the full thickness of the material. Due to the cross-linking of the surface, the hardness or rigidness of the article is increased, and said hardness or rigidness can be selectively provided to different parts of the article, by cross-linking the surface of certain parts of the article.
  • US 6709742 relates to elastic fibres, consisting of a polyolefin, for example polyethylene, and a photo-initiator in an amount sufficient to cause at least a partial cross-linking of the polymer, if the fibre is exposed to UV-radiation.
  • Articles made from fibres of said invention exhibit a good heat resistance and elasticity at high temperatures.
  • WO 2007/035875 A2 discloses a thermoplastic material made of caprolactone and being cross-linked by UV irradiation. The material is used for patient immobilization.
  • Document US 4 238 522 A discloses a composition comprising polycaprolactone and benzophenone. The polymer is cross-linked under UV irradiation. The material is used in the manufacture of splints, cast and patient's immobilization devices.
  • immobilization elements for immobilizing body parts have the ability to capture precisely the position and/or posture of the body part to be immobilized and to limit the ability to move the body part within acceptable limits, once immobilized.
  • immobilization element allows for a reproducible positioning in time in a very precise manner. This is particularly important in the case of fragmented treatments.
  • the polymer sheet is sufficiently flexible in order to ensure an adequate wear comfort.
  • the object of the present invention is to provide a method for producing a polymer sheet suitable for use as an immobilization element, or for the manufacture of immobilization elements, for the immobilization of one or more body parts.
  • the method of the present invention is characterized in that a polymer sheet, having a thickness of 1.0 to 5.0 mm, which is at least partly made of a polymer material comprising a polymer from the group of polycaprolactone, a copolymer of polyethylene with at least one ⁇ -olefin with 3-10 C atoms, or a mixture of two or more of the aforementioned polymers, and a photo-initiator, is at least partially cured by exposure to UV radiation for the at least partial cross-linking of the polymer.
  • cross-linking is meant the cross-linking of a polymer material, but also the hardening of a polymer material.
  • the inventor has found that the use of UV radiation offers the possibility to vary and control the degree of cross-linking of the polymer sheet and hence, the mechanical properties of the polymer sheet after the cross-linking has been achieved.
  • a higher degree of cross-linking usually leads to a polymer sheet with a higher toughness and rigidness, a higher modulus of elasticity in the molten state and less elasticity and a higher rigidity in the molten or softened state.
  • a lower degree of cross-linking usually leads to a polymer with a lower toughness and rigidness, a lower modulus of elasticity in the molten state, a higher stretchability and a higher rigidness in the molten or softened state.
  • This usually leads to a formed sheet of a smaller thickness.
  • the present invention thus provides the possibility to control properties such as modulus of elasticity, elasticity and rigidness of the polymer sheet in the molten or softened state by controlling the degree of cross-linking.
  • UV radiation offers important advantages compared to the use of ⁇ -radiation, known from the state of the art.
  • ⁇ -radiation leads to a uniform curing or cross-linking of the polymer material over the entire thickness of the polymer material
  • the use of UV-radiation provides the advantage that the penetration depth of UV radiation in the material can be controlled, and thus the degree of cross-linking or curing degree as a function of the penetration depth.
  • This offers the advantage that the flexibility and rigidity of the recrystallized material, as well as the stability of the immobilization element and the comfort provided to the patient can be varied and controlled.
  • the method according to the invention is suitable for the manufacturing of polymer sheets, made of polymer materials which are transparent for visible light, as well as polymer sheets, made of polymer materials which are transparent for non-visible light.
  • polymers transparent for UV radiation, such as copolymers of polyethylene, the UV penetration depth will usually be larger, and a more uniform degree of cross-linking as a function of the thickness and a higher uniformity in the mechanical properties over the entire thickness of the polymer will easily be realized.
  • Cross-linking by means of ⁇ -radiation and electron beam cross-linking is usually implemented in expensive devices, especially provided for that purpose, and which are normally not found on the location where the polymer sheets or the immobilization elements are produced, making the production process slow and complex and inflexible.
  • Cross-linking in the presence of peroxide often causes shrinkage and orientation of the polymer sheet when heating the sheet prior to forming the immobilization element over the body part.
  • UV radiation it is possible to treat the polymer sheets individually, on-site, and to control the degree of cross-linking of the individual sheets, taking into account the intended application, or on the other hand to simultaneously expose multiple sheets to UV radiation.
  • the method of the present invention further provides the possibility to reduce the UV penetration depth in polymers which are transparent for non-visible light, such as polycaprolactone, to the vicinity of the irradiated surface, such that a higher viscosity on the irradiated side of the polymer sheet can be obtained, and a higher elastic modulus in the molten state as a result of a larger degree of cross-linking, in comparison with the inside which is softer, and more thermo-formable, and which has a lower melting strength as a result of a lower degree of cross-linking.
  • polymers which are transparent for non-visible light such as polycaprolactone
  • the method of the present invention also offers the possibility to divide the polymer sheet into zones, and to subject different zones to a different degree of cross-linking.
  • a particular embodiment of the present invention is therefore characterized in that the polymer sheet at least comprises a first and a second zone, wherein the first and second zone have a different degree of cross-linking.
  • the polymer sheet is composed of a polymer material comprising
  • a polymer material which comprises polycaprolactone or a copolymer of polyethylene with at least one ⁇ -olefin having 3-10 C atoms is particularly suitable for the manufacture of a polymer sheet for use as an immobilization element.
  • These polymer materials are mouldable in the molten or softened state at low temperatures, tolerated by the body and the skin, such that the polymer sheet can directly be formed onto the body part to be immobilized.
  • the polymer sheet of the present invention particularly suitable for use as immobilization element in radiation therapy and diagnostic imaging, and in all other applications where a tight fit on the body part to be immobilized is of the utmost importance to provide an accurate positioning and repeatable re-positioning of the body part in the desired position, to enable a single treatment or an intermittent or fractionated treatment.
  • a photo-initiator in the context of the present invention, with a photo-initiator is meant a chemical composition which, when exposed to UV light, generates radicals on the polymer chains and initiates cross-linking of the polymer.
  • a wide range of photo-initiators may be used.
  • the photo-initiator is selected from the group of benzoin, substituted benzoins such as benzoin ethyl ether, benzophenone, benzophenone derivatives, Michler's ketone alfa-hydroxyketone, benzil dimethyl ketal, isopropyl thioxanthane, dialkoxyacetophenones such as diethoxyacetophenone, acetophenone, benzil, and other derivatives and mixtures thereof.
  • benzoin substituted benzoins such as benzoin ethyl ether
  • benzophenone benzophenone derivatives
  • Michler's ketone alfa-hydroxyketone benzil dimethyl ketal
  • isopropyl thioxanthane isopropyl thioxanthane
  • dialkoxyacetophenones such as diethoxyacetophenone, acetophenone, benzil, and other derivatives and mixtures thereof.
  • Benzophenone is
  • concentration of the photo-initiator in the polymer material can be varied within wide limits. The most favourable concentrations and ratios may be determined empirically by varying the composition and exposing the polymer sheet to UV radiation to obtain, for the intended application, the optimum physical and chemical properties of the at least partially cross-linked polymer material. In general, the concentration of photo-initiator is between 0.1 and 5.0 weight%, and preferably between 0.2 and 5.0 weight%, based on the weight of the polymer material.
  • the polymer material also comprises an amount of a photo-cross-linker.
  • a chemical composition is meant that, in the presence of a photo-initiator, accelerates and promotes the cross-linking of the polymer. This allows the production of a polymer sheet to be accelerated.
  • a wide range of photo-cross-linkers which, when generating free radicals, are able to link two or more polymer chains through the formation of covalent bonds, may be used in the present invention.
  • these photo-cross-linkers are polyfunctional, that is to say that they have two or more reactive functional groups which, when activated, are capable of forming a covalent bond with a functional group on the polymer.
  • Photo-cross-linkers with a low melting temperature ( ⁇ 100 - 120 °C) and a good compatibility with polycaprolactone and a copolymer of polyethylene with at least one ⁇ -olefin having 3-10 C atoms are preferred.
  • triallyl cyanurate is particularly preferred.
  • Other examples of suitable photo-cross-linkers may be selected from the group of polyfunctional vinyl or allyl compounds such as triallyl cyanurate, triallyl isocyanurate, pentaerthritol tetramethacrylate, ethylene glycol, dimethacrylate, diallyl maleate, dipropargyl monoallyl cyanurate, and other derivatives and mixtures thereof.
  • the concentration of the photo-cross-linker in the polymer material may be varied within wide limits, but preferably ranges between 0.01 and 2.0 weight% , based on the weight of the polymer material.
  • the polymer material may also comprise other components to change the mechanical properties of the polymer sheet, if this is of interest for the intended application.
  • the at least one ⁇ -olefin with 3-10 C atoms is selected from the group of a copolymer of ethylene and 1-butene or 1-octene or a mixture of two or more of these copolymers.
  • the inventors have found that these plastic materials are mouldable at a low temperature. This renders the polymer sheet of the present invention particularly suitable for use in radiation therapy and diagnostic imaging and in all other applications where a precise repositioning of the immobilization element in intermittent treatment is of the utmost importance.
  • the polymer sheet offers, for use as immobilization element, more comfort to the patient, because it feels soft to the skin and has a higher flexibility and lower rigidness, even after complete crystallization, in comparison with the already known immobilization elements. As a result of the reduced rigidness, the material can easily be cut with a good and smooth finish of the edges with conventional tools such as scissors and knives.
  • the polymer material comprising polycaprolactone or a copolymer of polyethylene with at least one ⁇ -olefin having 3-10 C atoms, a photo-initiator and a photo-cross-linker, can be prepared in any manner known to the skilled person, for example, by mixing or combining the ingredients by mechanical stirring, by a sonication treatment, or by means of a melt mixer. Manufacturing a polymer sheet on the basis of this composition may be done by any technique deemed suitable by the skilled person. Preferably, the forming of the polymer material into a sheet is done by means of extrusion, in particular flat extrusion.
  • the polymer sheet prior to the exposure to UV radiation is preferably cut into a desired shape.
  • This offers the advantage that the waste material is not cross-linked and can be recovered for recycling. Since the polymer material is relatively expensive, and an average of up to 30% of the material is lost as waste when cutting and perforating, this is an important advantage.
  • the cutting of the polymer sheet and the cross-linking of the sheet can be combined in a process, wherein, in a first step, the polymer sheet is cut into the desired shape, and subsequently exposed to UV radiation for cross-linking of the polymer sheet. It was found that the time, required for cutting the sheet into the desired shape, can be tailored to the time required for cross-linking the polymer to the desired degree of cross-linking.
  • Perforation may be carried out before or after the exposure to UV-radiation. Usually, perforation is carried out prior to exposure to UV radiation to better achieve a better uniformity in the cross-linking and to allow recycling of perforation material.
  • Perforation may extend over the entire sheet, or may be limited to specific areas in the surface direction of the polymer sheet. Perforations will usually extend through the entire thickness of the sheet. The perforations may be applied randomly or according to a certain pattern. The dimensions of the perforations in the polymer sheet will usually range between 0.5 and 3.0 mm, preferably between 1 and 2 mm. According to the invention, all perforations may approximately have the same dimensions, or perforations of varying dimensions may be used at random or in different zones. The latter offers the possibility to locally change the elasticity of the polymer sheet. The presence of perforations offers many advantages, including the fact that the immobilization element is lighter and allows evaporation of moisture through the immobilization element.
  • the polymer sheet used in the process of the present invention, preferably has a thickness which is adapted to the intended use.
  • the thickness of the polymer sheet preferably ranges between 1.0 and 5.0 mm. Often a thickness of about 1.6 - 3.2 mm is used. With such a thickness, the desired degree of cross-linking can be obtained by exposing the polymer sheet on both sides, to UV radiation.
  • the duration of the irradiation with UV, and the energy of the UV radiation source may be varied within wide limits, and is preferably chosen such that the desired degree of cross-linking is achieved without degradation of the polymer sheet to occur.
  • the sheet is exposed to UV radiation, preferably for a period of time of 30 seconds to 1 hour at a radiation power of 10 watts to 500 watts. It is to be expected that with a higher radiation power, a shorter period of time is required.
  • the skilled person is capable of matching the radiation intensity and duration to the intended degree of cross-linking, taking into account the thickness of the polymer sheet and the transparency of the sheet for UV radiation.
  • the skilled person may irradiate the polymer sheet on both surfaces, facing each other.
  • UV radiation is meant that the wavelength of the radiation ranges between 100 and 450 nm, more preferably between 280 and 400 nm.
  • the photo-initiators which are preferred within the scope of the present invention, attain their maximum efficiency.
  • the most appropriate wavelength is chosen taking into account the thickness of the polymer sheet, the nature of the polymer material and the nature of the photo-initiator. It is generally known that UV radiation with a longer wavelength penetrates more deeply, and hence allows cross-linking a thicker polymer sheet. Irradiation with UV light may be carried out on one surface of the polymer sheet, or on both surfaces, facing each other.
  • Suitable UV sources comprise conventional UV lamps, typically Hg lamps, which span a wide continuous band of the UV spectrum, usually between 200 and 450 nm. They may develop high powers, but this is accompanied by a significant warm-up, which can lead to the melting of the polymer sheet. Therefore, it may be necessary to cool the polymer sheet, for example by means of a cold air or gas flow. LED lamps have the property that they span a narrow discrete band of the UV spectrum, often in the wavelength range of 365 or 395 nm. LED lamps have a lower power such that cross-linking is slower, but it is better controllable.
  • a lower power can be overcome by decreasing the distance between the light source and the polymer sheet, or by using the light source in combination with a photo-initiator with a high efficiency.
  • the skilled person will take into account, when selecting the source of the UV radiation, the requirements of the application. Suitable LED lamps are commercially available from various suppliers.
  • the present invention also relates to a non-invasive immobilization element obtained by the method described above.
  • the present invention further relates to a non-invasive immobilization element for the immobilization of one or more body parts in a predetermined position, wherein the immobilization element comprises a sheet which is at least partly made from a polymer material, comprising an at least partially cross-linked polymer selected from the group of polycaprolactone, a copolymer of polyethylene with at least one ⁇ -olefin having 3-10 C atoms, or a mixture of two or more of the aforementioned polymers, and a photo-initiator, wherein the polymer sheet has a thickness of 1.0 to 5.0 mm. Further technical characteristics of the immobilization element are as described above.
  • the polymer sheet has a degree of cross-linking which decreases from a surface of the polymer sheet in the thickness direction of the polymer sheet.
  • the polymer sheet comprises at least a first and a second zone, wherein the first and second zone have a different cross-linking.
  • the immobilization element as shown in Figure 1 is placed on the skin of the body part to be immobilized of the patient in such a way that the body part is enclosed by the immobilisation element, and is incorporated therein.
  • the edges of the immobilization element are attached to a table on which the patient is located in order to immobilize the body part in the desired posture and the desired position.
  • the polymer sheet shown in Figure 2 exhibits a mask zone 1 which is intended to cover the face of the head, a first, second and third connection zone 2a, 2b and 2c which are intended for connecting the mask zone with a support on which the patient is located and thus to oppose movement of the head as good as possible and to limit it to a maximum of 1-2 mm.
  • the mask zone 1 and the connection zones 2a, 2b, 2c may show the same or a different degree of cross-linking.
  • the connection zones 2a, 2b, 2c may exhibit a mutually similar or a different degree of cross-linking.
  • the connection zones 2a, 2b, 2c have a higher degree of cross-linking, and the mask zone 1 has a lower degree of cross-linking.
  • the polymer sheet is heated to a temperature in the range of the melting or softening temperature. The thus melted or softened sheet is applied to the body part to be immobilized and formed thereon, preferably in such a way that the sheet adopts as well as possible to the contours of the body part to be immobilized.
  • connection zones into two or more zones, and to give different zones a different degree of cross-linking.
  • a lower degree of cross-linking in the mask zone 1 leads to a polymer with a lower toughness and rigidness, lower modulus of elasticity and a higher rigidness and lower stretchability in the molten or softened state.
  • the higher stretchability offers the possibility to significantly reduce the thickness of the polymer sheet in comparison with a sheet with a higher degree of cross-linking, and thus to provide a mask zone 1 with a somewhat higher flexibility, even after cooling and crystallization, and a smaller thickness.
  • the mask zone 1 it is further possible to divided the mask zone 1 into two or more zones, and to give different zones a different degree of cross-linking.
  • connection zones 2a, 2b, 2c A higher degree of cross-linking in the connection zones 2a, 2b, 2c leads to a higher toughness and rigidness, a higher elasticity modulus and lower stretchability in the molten or softened state.
  • the lower stretchability of the connection zone counteracts stretching of the connection zone and usually leads to connection zones with a higher thickness, which is rigid and provides stability to the immobilization element.
  • Dividing the polymer sheet into two or more zones provides the ability to individually control the degree of cross-linking of the zones, and to control the mechanical properties of the individual zones, taking into account the function they perform in the immobilization element.
  • both the mask zone 1 and the connection zone 2a, 2b, 2c are perforated.
  • the mask zone 1 may or may not be perforated, and the connection zones 2a, 2b, 2c may or may not be perforated.
  • the mask zone 1 may have the same degree of perforation and perforation pattern as the connection zones 2a, 2b, 2c, or a different one.
  • the connection zones 2a, 2b, 2c may exhibit the same degree of perforation and perforation pattern or a different one.
  • a uniform perforation can be used.
  • connection zone a uniform perforation to be applied, or the connection zone can be divided into further zones, which have a different degree of perforation.
  • the size of the perforations in each zone to be controlled, as well as the number of perforations applied and the perforation pattern.
  • the adjustability of the degree of cross-linking and the degree of perforation makes it possible to vary and to control the mechanical properties of an immobilization element within wide limits.
  • the division into zones allows the mechanical properties of each zone of the immobilization element to match the function performed by that zone.
  • Polymer sheets having a composition as listed below were prepared by cross-linking by exposure to UV radiation of a single sheet of polymer material which comprises either polycaprolactone (Capa), obtained from Perstorp UK Ltd, or a polyolefin elastomer, obtained from Dow, as well as a photo-initiator (benzophenone), obtained from Ciba, a photo-cross-linker (TAC) and a colour master batch.
  • the composition of the polymer sheets is shown in Table 1.
  • Table 1 shows the composition of a sample containing polycaprolactone (Capa), TAC and benzophenone, and a sample that contains a polyolefin elastomer, TAC and benzophenone, as well as a colour master batch.
  • the polymer sheets were manufactured by extruding the Capa or the polyolefin elastomer together with the photo-initiators, the photo-cross-linker in a ZSK 18 twin screw extruder (Coperion).
  • the polymer material that is obtained in this way, was formed into a sheet by means of press moulding, using an hydraulic press of Agila model PE30.
  • the polymer sheets were cross-linked by exposure to UV radiation.
  • UV lamps with a power of 18 W at a wavelength of 370 nm.
  • the duration of the exposure to the UV radiation for the different polymer sheets is shown in Tables 2 and 3.
  • the degree of cross-linking of the polymer sheets was assessed by means of two measuring methods : 1) oscillation rheometry 2) RTS (resistance to stretch).
  • the oscillation rheometry was performed with an Anton Paar Rheometer MCR 300. With the oscillation rheometer, used at a frequency of 0.01 to 10.0 Hz for a sample with standard dimensions, cut from the polymer sheet, the complex viscosity, the storage modulus and the loss modulus were determined, which increase as a function of the degree of cross-linking of the polymer sheet and therefore allow to estimate the degree of cross-linking.
  • the measurements were carried out at a temperature of 70 °C.
  • RTS resistance to stretch
  • the results for the oscillation rheometry measurements are shown in Table 2 and the results for the RTS measurements in Table 3.
  • Table 1 Composition of the polymer samples.
  • Sample 1 Composition (%) Capa 83.5 TAC Master batch 12.0 Colour Master batch 3.0 Benzophenone 1.5
  • Sample 2 Polyolefin elastomer 85.0 TAC Masterbatch 12.0 Benzophenone 3
  • Table 2 Results of the oscillation rheometry measurements for the polymer samples. Thickness (mm) Curing (hours) Comp.visc. (Pa.s) Storage Mod. (Pa) Loss Mod.

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BE2011/0752A BE1020363A3 (nl) 2011-12-23 2011-12-23 Werkwijze voor het vervaardigen van een polymeer vel voor gebruik als immobilisatie element.
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